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Lattice-sulfur-impregnated zero-valent iron crystals for long-term metal encapsulation

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Abstract

Using nanoscale zero-valent iron (nFe0) materials for heavy metal removal is a viable approach for in situ groundwater pollution remediation. However, conventional nFe0 materials have indiscriminate reactivity towards various electron acceptors (for example, water) and just accumulate heavy metals onto the surface, which leads to poor selectivity and short longevity. Here we develop a lattice-sulfur-impregnated nFe0 (S-nFe0), achieving intraparticle sequestration of heavy metals enabled by a boosted Kirkendall-like effect. This metal-encapsulation approach outcompetes water for electrons and efficiently uses Fe-released spots, and the reacted S-nFe0 becomes inert to release metals (78–220× less than nFe0) in real groundwater matrices. The treated groundwater is estimated to meet drinking-water standards with a longevity of over 20–100 years. The synthesis of S-nFe0 has negligible environmental impacts according to Biwer–Heinzle environmental evaluation results. S-nFe0 also shows competitive production and operation costs for metal-contaminated groundwater remediation. Overall this work presents a strategy for achieving metal encapsulation in nFe0, which breaks the reactivity–selectivity–stability trade-offs of redox nanomaterials, providing a powerful tool to tackle groundwater pollution.

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Fig. 1: Sulfur-impacted distributions and incorporations of heavy metals over nFe0 nanoparticles.
Fig. 2: S-induced lattice expansion, electron-density redistribution and Fe dissolution in Fe0 bcc structure.
Fig. 3: Evolution of elemental distributions and relevant depth profiles of metals on the surface and subshell of FeS2-nFe0.
Fig. 4: Long-term application-potential and economic–environmental feasibility assessments of FeS2-nFe0 for metal encapsulations.

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Data availability

All data supporting the results of this study are available within the paper and its Supplementary Information. Source data are provided with this paper.

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Acknowledgements

This work was supported by the National Key Research and Development Program of China (2021YFA1202700), National Natural Science Foundation of China (22206165, 22193060 and U21A20163), the Key Research and Development Program of Zhejiang Province (2024C03228) and JSPS KAKENHI (number JP23K13703). We acknowledge Beijing Paratera Tech for providing HPC resources.

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Authors and Affiliations

  1. College of Environmental and Resource Sciences, Zhejiang University, Hangzhou, China

    Chaohuang Chen, Qianhai Zhou, Zhongyuan Guo, Chen Miao, Du Chen, Xiaohong Hu, Xia Feng, Lizhong Zhu, Daohui Lin & Jiang Xu

  2. Zhejiang Provincial Key Laboratory of Organic Pollution Process and Control, Zhejiang University, Hangzhou, China

    Chaohuang Chen, Qianhai Zhou, Zhongyuan Guo, Chen Miao, Du Chen, Xiaohong Hu, Xia Feng, Lizhong Zhu, Daohui Lin & Jiang Xu

  3. Advanced Institute for Materials Research (WPI-AIMR), Tohoku University, Sendai, Japan

    Hao Li

  4. Stanford Synchrotron Radiation Lightsource, SLAC National Accelerator Laboratory, Menlo Park, CA, USA

    Vincent Noël

  5. Department of Civil Engineering, McGill University, Montreal, Quebec, Canada

    Subhasis Ghoshal

  6. Department of Civil and Environmental Engineering, Carnegie Mellon University, Pittsburgh, PA, USA

    Gregory V. Lowry

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  1. Chaohuang Chen
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Contributions

C.C., Z.G. and J.X. designed research. C.C., Q.Z., D.C., X.H. and X.F. synthesized materials, performed experiments and analysed data. Z.G., C.M., H.L. and V.N. contributed advanced analytic tools and relevant analysis. S.G. and G.V.L. discussed the results and edited the article. D.L. and L.Z. secured funding, provided analytical tools and commented on the article. J.X. supervised the entire project.

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Correspondence to Jiang Xu.

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Nature Sustainability thanks Zhihui Ai, Xiaohong Guan and Yun Wang for their contribution to the peer review of this work.

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Supplementary Texts 1–7, Figs. 1–27 and Tables 1–9.

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Source Data Fig. 1

XRD patterns of metal-reacted material, standard redox potentials of metals and Ksp of metal sulfides.

Source Data Fig. 2

XRD patterns of fresh material and the linear scan intensity of metal-reacted FeS2-nFe0.

Source Data Fig. 3

XPS of metal-reacted FeS2-nFe0.

Source Data Fig. 4

Removals of metals by macroscale synthesized FeS2-nFe0 and assessments of production-remediation costs.

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Chen, C., Zhou, Q., Guo, Z. et al. Lattice-sulfur-impregnated zero-valent iron crystals for long-term metal encapsulation. Nat Sustain (2024). https://doi.org/10.1038/s41893-024-01409-4

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